Method for preparation of nitrophenols



peroxides and more particularly to that class of hydro- United States Patent METHOD FOR PREPARATIGN 0F NITROPHENGLS JoshuaC. Conner, Jr., Wilmington, Del.,.assignor to Hercules, Powder Company, Wilmington, Del., acorporationofDelaware No Drawing. Originalr application October 5, 1950, Se- !'ial'N0...18 8,645, now Patent No. 2,718,530, dated-September-20,1955. Divided andthis applicationJune'9, 1954, Serial No.-435,625

9. Claims. (Cl. 260-622) This invention relates to a new class of organic hydroperoxides containing a hydroperoxy group attached to a carbon atom which is adjacent to an aromatic ring containing nitro substitutents.

In view of the inability of the organic hydroperoxides of the prior art'to serve in certain applications, there has been a need'for a new class of organic hydroperoxides which would have a different reactivity than the-hydro peroxides of the art and which, therefore, wouldovercome some of the disadvantages of the hydroperoxides which have heretofore been prepared.

Now in accordance with this invention there has been discovered a class of hydroperoxides which has great commercial utility. This class of hydroperoxides is characterized by containing an aromatic hydrocarbon nucleus having. attached to the ring thereof at least one nitro group and at least one member of the group consisting of ogcrdialkyl a-hYdlOPGI'OXYDlClZhYl and oc-alkYl-oc-hYdIO- peroxymethyl groups. The hydroperoxides of this invention may-be prepared by passing an oxygen-containing gas under noncatalytic conditions through the corresponding nitrated hydrocarbon in liquid phase. nitrocumene can ,be oxidized to a,a-dimethyl-p-nitrobenzyl hydroperoxide by passing oxygen through this compound in the liquid phase at a temperature of, for example, between about 20 C. andv 200 C. in the presence of an aqueous solution of a water-soluble alkali. 'Ihe hydroperoxides of this invention are particularly useful in that they may be decomposed to produce nitrophenols and either aliphatic ketones or aliphatic aldehydes simply, efiiciently, economically, and simultaneously. The decomposition process is straightforward and is capable of producing nitrophenols of definite structure while at the same time producing either aliphatic ketones or'aliphatic aldehydes as valuable products. This is in contrast to previous processes for preparing nitrophenols.

In carrying out the decomposition of the hydroperoxides of this invention, the hydroperoxides, such as a,a-dimethyl-p-nitrobenzyl hydroperoxide, which maybe dissolved in a solvent such as cumene 0r benzene, iscontacted with a catalyst such as an acid-treated bentonite at a temperature of about 20 C. until the hydroperoxide is completely decomposed to the nitrophenol. Thenitrophenol produced is p-nitrophenol and theother product of the decomposition reaction is acetone which isrecovered in suitable condensation units which are part of the apparatus used. The following examples constitute specific illustrations of the products of this invention, methods for preparing these products and processes in which the products of the invention may be utilized to prepare other useful products. All parts are parts by weight.

Example 1 Into a glass reaction vessel equipped with a stirrer, a refluxcondenser, and an oxygen-inlet tube were charged 100 parts of p-nitrocumene (n =1.532l; N=7.93), 3.1 parts of'an a,a-dimethylbenzyl hydroperoxide product For example, p-

2,774,796 Pate t d Dec. 18, 19 5s containing 97.6% of thee-hydroperoxide and 200 parts of an 0.5% aqueous sodium hydroxide solution. The reactionvmixture washeated'to C.*and'. oxygen was passed through the mixture at a rateof cc..p.er minute. .Duringthe oxidation, samples were withdrawn at regular intervals 'for determination of hydroperoxide content, the determination being carried out by adding the sample to an acidified potassium iodide solution and noting the amount of. iodine liberated. The log oftherun was as follows:

Percent a, a-Dimethyl- Time,- Hrs. m p-Nltrobenzyl Hydroper: oxide Upon completion of the oxidation there was" recovered 75 artsof'a'bright yellow product which contained u,adimethyl-p-nitrobenzylhydroperoxide as the-principal oxy-' genated material. Material recovery from the oxidation, including samples withdrawn for analysis, was about 93% Example v2 The-procedure otExamplel-was duplicated with the exception that there was used '3 00 parts of p-nitrocumene N=8.-65-), 39.3-partstofxan a,u-dimethyl-p-nitrobenzyl hydroperoxidewproducti containing 22.1 of the hydroperoxide and 200 parts of an 0.5'% aqueous sodium hydroxide solution. The log of the run was as follows:

Percent a, a-Dimethyl- Time, Hrs. 1:0 p-Nltrobenzyl Hydroperoxide Uponcompletion ofthe oxidation there was recovered 322 partsof a liquidproduct containing a,a'-dimethyl-p-' nitrobenzyl'hydroperoxide as the principal oxygenated material. 'Material'recovery, including samples withdrawn for analysis; was about 97%.

Example .3

In this example, mononitrodiisopropylbenzene (2-nitro- 1,4-diisopropylbenzene) in the xamount of 500 parts was oxidized underanhydrous-conditions at a temperature of 100 Cinthe-presence otSparts of calcium hydroxide and 5 0 parts of a-,a=dimethylbenzyl.hydroperoxide product containing- 10% of the hydroperoxide by. passing 1 oxygen through themixtureat .aurate of 0.15 cu.,ft.:/nj1in. After six hours it was found that the yellow reaction product contained 27.7% of 2-nitro-4-isopropyla,-dimethylbenzyl hydroperoxide.

Example 5 parts of 2-nitro-1,4-diisopropylbenzene was oxidized in the presence of 2 parts of an o e,e',m'-tetramethyl-p-xylylene dihydroperoxide product containing 50% of the 9 hydroperoxide, and 50 parts of a 2% aqueous sodium carbonate solution. The reaction mixture was heated to 110 C. and air was passed through the mixture under a pressure of 80 p. s. i. for 60 hours. Upon completion of the oxidation, there was recovered 80 parts of a bright yellow product which was identified as 2-nitIO-ot,a,oz',ot'- tctramethyl-p-xylylene dihydroperoxide.

Example 7 Following the procedure of Example 6, 200 parts of 2,4-dinitroisopropylbenzene was oxidized for 48 hours at 100 C. in the presence of 50 parts of a 1% sodium carbonate solution. The oxidation was initiated with one part of 2,4-dinitro-a,a-dimethylbenzyl. hydroperoxide. The yellow-orange oxidation product contained 35% of 2,4-dinitro-u,a-dimethylbenzyl hydroperoxide.

Example 8 In this example, p-nitro-a,a-dimethylbenzy1 hydroperoxide was decomposed under anhydrous conditions. To a reaction vessel equipped with a stirrer, a condenser, and an inlet for addition of the hydroperoxide there was charged 50 parts of the 26.8% hydroperoxide product obtained in Example 2 over a -minute period to an agitated slurry of 0.6 part of an acid-treated bentonite in 8 parts of benzene. The temperature was regulated to keep the benzene at reflux. Ten minutes after the addition of the hydroperoxide was completed an active oxygen analysis of the reaction product, obtained by adding a sample of the reaction mixture to acidified potassium iodide, indicated that the hydroperoxide had been completely decomposed. The acetone and benzene were then removed by distillation at atmospheric pressure and a vapor temperature of 74 C., 12.1 parts of the distillate containing 30.9% acetone. This quantity corresponded to a 95.6% yield of acetone based on the hydroperoxide originally present. The residue was extracted with 5% aqueous sodium hydroxide solution until a negative test for phenolic material was obtained. The aqueous extracts were combined, acidified with hydrochloric acid and extracted with ether until the aqueous residue gave a negative test for phenol. Evaporation of the ether extract yielded l0.1 parts of red crystalline p-nitrophenol, which corresponded to a yield of 98% based upon the hydroperoxide originally present. Analysis of the product showed a nitrogen content of 9.53% which was 95.3% of the theoretical.

Example 9 In this example, m-nitro-a,u-dimethyl-p-methylbenzyl hydroperoxide was decomposed in an: aqueous system. Fifty parts of an m-nitro-u,u-dimethyl-p-methylbenzyl hydroperoxide product containing 75% of the hydroperoxide was added to 50 parts of 10% aqueous sulfuric acid solution-and rapidly stirred at 100 C. After 70 minutes the hydroperoxide was complely decomposed. The reaction mixture was neutralized with 16 parts of sodium hydroxide in pellet form and distilled until 25 parts of distillate was obtained. Analysis of the distillate by means of the well known 2,4-dinitrophenylhydrazine method showed a 92% yield of acetone based on the quantity of hydroperoxide originally present. The residue was extracted with two portions of ether, acidified with concentrated hydrochloric acid and then further extracted with three more portions of ether. The combined ether extracts when evaporated to dryness gave a yield of yellow crystalline m-nitro-p-cresol, which was 75% of the theoretical based on the hydroperoxide orgiinally present.

The examples have set forth nitrocumene, nitro-p-cymene, dinitrocumene, nitroethylbenzene, and nitrodiisopropylbenzene as compounds which may be oxidized to produce the hydroperoxides of this invention and it will be realized that the hydroperoxides of this invention may be prepared by the oxidation of any organic compound containing an aromatic hydrocarbon nucleus having attached to the ring thereof at least one nitro group and at least one alkyl group having at least two carbon atoms. The basic hydrocarbons corresponding to the nitro derivatives which are oxidized in accordance with this invention may be illustrated by such compounds as cumene, p-cy mene, p-diisopropylbenzene, isobutylbenzene, secondary buty lbenzene, tertiary butylisopropylenbenzene, p-ethylisopropylbenzene, ozor fi-isopropylnaphthalene, ethylbenzene, n-propylbenzene, n-butylbenzene, and n-amylbenzene. These compounds all contain either a secondary or tertiary carbon atom adjacent to the aromatic nucleus. The aromatic nucleus need not be deirved from benzene, as is the case of cumene, since compounds containing aromatic nuclei, such as those derived from napthalene, anthracene, and phenanthrene may also be oxidized in accordance with this invention to produce the correspond ing hydroperoxides. Other alkyl groups which may be attached to the aromatic nucleus are the methyl, ethyl,

propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl and the like. When more than one alkyl group is attached to the aromatic nucleus these alkyl groups may be either the same or different and may be any of the alkyl groups mentioned above. The alkyl groups attached to the u-carbon atom of the compound (i. e., the carbon atom to which the hydroperoxy group is attached) also may be the same or difierent and may be any of the above-named alkyl groups.

The compounds which are oxidized in accordance with this invention are those hydrocarbons discussed above which contain one or more nitro substituents attached to the aromatic nucleus. When the aromatic nucleus is phenyl, the number of nitro substituents generally will not exceed three and one or two such substituents are preferable. The same holds true for nuclei such as naphthylanthryl, and phenanthryl, though a greater number of nitro substituents are possible in such nuclei due to the greater number of free positions. Specific compounds which may be oxidized to corresponding hydroperoxides are p-nitrocumene, 2-nitro-1-methyl-4-isopropylbenzene, 3-nitro l methyl-4 isopropylbenzene, m-nitrocurnene, 2,4 dinitroisopropylbenzene, 2,4,6 trinitroisopropylbenzene, 4 nitro 1 isopropylnaphthalene, p-nitroethylbenzene and 2 nitro 1,4 diisopropylbenzene. Other compounds which may also be oxidized to produce the hydroperoxides of this invention are nitrodiisopropylbenzene, nitrotriisopropylbenzene and similar compounds having more than one nitro group and more than one alkyl group attached to the ring of the hydrocarbon nucleus. In the case of those compounds having more than one alkyl group attached to the hydrocarbon nucleus, oxidation of these compounds in accordance with this invention for an extended period leads to the formation of polyhydroperoxides such as the dihydroperoxides and the trihydroperoxides. Thus, when mononitrodiisopropylbenzene is oxidized for an extended period of time there is produced the dihydroperoxide c'o'irespondingtothis compound, the hydroperoxy group's"'bei'ngattached tothe tertiary carbon atoms offthe isoprop'ylgroups. "'In'the case of the extendedoxidation'of acompound such as 1 nitro-2-ethyl-4 isopropylbenzene, there"results "the dihydr'operoxide of this compound with the' one 'hydroperoxy group attached to the tertiarycarbon atom ofthe isopropyl group "and the other hydroperoxygroup attached to the secondarycarbonatomof the ethyl group.

The process for producing 'the"hydroperoxides of" this invention essentially comprises passing an oxygen containing gas under no'ncatalytic conditions throughthenitro-substituted aromatichydrocarbons" discussed above,- the oxidation being'carried out in'theliquid phase. The liquid phase may be either substantially homogeneous,- as when anhydrous conditions are used "and" thecompound being oxidized is the 'pri'ncipal'compo'nent of the" reaction mixture, or it may be heterogeneousfas when aseparate aqueous'phase,whichmay be either'ordinary water oran aqueous alkaline solution, is included.

'The temperature during oxidation will be in excess of 20 C. Using anhydrous conditions, the temperature range is preferably fromabout 50 to'about 100 C., more desirably from'about 65 to about'90 C. Particularly satisfactory isthe range between about 75 and about 90 C. When'using an aqueous'phaseflhe temperature is preferably between'about 25 and about 95 C., desirably between about 50"and about 90 C. When pressure is applied to the'oxidation system, however, the temperature may beincreased considerably, for example, up to about'200 C. Under anhydrous conditions using pressure the preferable range is from about 50 to about 150 C., and when using an aqueous phase andpressure, it is most desirable to operate between about 95-and about 200 C.

The pressures which can be utilized during those oxidations'carri'ed'out-at greater than atmospheric pressure are limited only by equivalent design. From a practical standpoint,'pressures from atmospheric up to about 500 p. s. i. arefeasible. "Pressures'between about 30 and about 500p. s i. "are advantageous, and pressures'of about'50 to about200 p. s. i. are preferable.

It is preferable that the'oxidationbe efiected using an alkaline stabilizin'g'agent. The examples'haveshown the use of sodium hydroxidea'nd calcium'hydroxide, but in general there'may be used the alkali' metal hydroxides, such as the hydroxidesofsodium,potassium, lithium, and the like; alkaline earth metal oxides-and hydroxides, such as calcium'hydroxide, barium hydroxide, strontium 'hydroxide, calcium'oxide, and barium oxide. Inorganic carbonates and bicarbonates, such as sodium carbonate and bicarbonate, and alkali metal salts of weak organic acids may also be employed. Strong organic bases such as trialkylarylammonium hydroxides, for example; trimethylbenzylammonium'hydroxide, may also be used. Ammonia also is operable. These alkaline stabilizing agents may be used either inthe form of an" aqueous solution or as part of an anhydrous oxidation reaction mixture. When used under anhydrous conditions, the alk'ali'preferably is in finely-divided form, and the amountmay be varied from about 0.05 to about 10% by weight based on the nitro-substituted aromatic organic compound being oxidized. A preferable range on this basis is from about 1 to about 5%, and a most desirable range is from about 1 to about 3%. When used in the form of an aqueous solution, the solutionwill contain between about 0.01 and about 35% by weight of the alkali. Preferably, the concentration of alkali in solution will be between about 0.01 and about 2%, and a highly desirable range is from about 0.5 to about 1.0% by weight. The ratio of the quantity of aqueous alkaline solution present in the reaction mixture to the amount of compound subjected to oxidation may be varied within wide limits from about 1:50 to about :1. It is preferable, however, to utilize a ratio within therange of from about 1:10 to about 1:3.

Another of the featuresof this invention is thestep of carrying out the oxidation'in the presenceof a'peroxidic' free radical oxidation initiator. Representative of such aninitiator is an a,a-dialkylarylmethyl 'hydroperoxide, for example, edimethylbenzyl hydroperoxide. In general, theremay-beused anyperoxidic substance which is-capable of initiating'a free radical oxidationchain under the conditions utilized. There may be used, in other words, any organic peroxide,hydroperoxide,- or compound capable of decomposing to form organic free radicals. Illustrative of such materials are acetyl peroxide, benzoyl peroxide, triphenylmethyl peroxide, tertiary butyl hydroperoxide tetralin hydroperoxide and naphthene hydroperoxides. These'peroxidic materials include the=acyl, aroyl, dialkyl, and'diaralkyl peroxides a'nd'thealkyl, aralkyl, cycloalkyl, and cycloalkenyl hydroperoxides. Other free radical initiators, such as hexaphenyl ethane, which are converted into peroxidic materialsduring the oxidation process of this invention-' also ar'eoperable. On the basis of the -pure peroxidic material,-'"the concentration of this material based on the compound being oxidized maybe varied from about 0.01 to about 20%, a preferable. range being from about 0.1 to about 10%. A particular applicable amount is about 3%. *When initiating theoxidation of the nitro-substituted aromatic organic compounds of this invention it may be desirable to use as the initiator the hydroperoxide obtained by oxidation of the same compound. For example in' the oxidation of p-nitrocumene it is preferable-to initiate the reaction by the addition of a,a-'dimethyl-p-nitrobenzyl hydroperoxide.

' The 'examples have set forth the use of oxygenas the oxygen-containing gas, but air. may be. utilized, and also operable are mixtures of :oxygenwith nitrogen or other inert gases. Therateiof input ofthe oxygen-containing gasshould be such thatuatleast the theoretical amount of oxygen is supplied. By i-th'eoretical amount is meant that amount of oxygen necessarywto convert the nitrosubstituted aromatic organic compound completely. to the corresponding hydroperoxide. Actually, it is preferable to use about twice the'theoretical amountof oxygen, and under such conditionsthe amount of oxygen in the exit gas will be about one-half of that in the input gas. The rate of input Will/depend upon the temperature and pressure utilized during the oxidation. Using p-nitrocumene as an example, itis possible to determine the rate: of oxidation of this compoundatany particular temperature and pressureand, knowingthe rate of oxidation, it then is possible to calculate the'amount of oxygen-necessary to get the required rate. Thisamoun-t of oxygen is the theoretical amount. In general, the rate of input at atmospheric pressurewill be from about lto about li-ters/hr./ kg. of the compound being oxidized, and under pressures of, 'for example, 50 to 200 p. s. i., will be from about 50 to about 350 liters/hr./kg. of the compound.

The oxidationprocess of this invention may be carried out either bat-chwise or continuously. It aifords a means ofobtaining high yields of the nitro-substituted hydroperoxides previously described. These hydroperoxides are extremely useful in that they may be decomposed to the corresponding nitro-substituted phenolic compounds. For example, p-nitrophenol may be prepared from 00,04- dime'thyl-p-nitrobenzyl hydroperoxide by action of an acid condensation catalyst such as sulfuric acid or an acid clay on the hydroperoxide. The reaction is one of decomposition of the hydroperoxideand results in the formation of p-nitrophenol and acetone. 'Due to the fact that the hydroperoxides of this invention contain their 'substi-tuent groups in definite relationship to each other, it is possible through decomposition of the hydroperoxides to obtain nitrophenols which contain the phenolic and nitro substituents in definite relationship to each other. The 'novel hydroperoxides of this invention therefore alford a'means of obtaining certain nitrophenols which have in the past always been prepared in admixture with other isomers.

- 'In carrying-out .the decomposition process ofthis invention, several difierent modifications of the nitrated hydroperoxides may be used. The hydroperoxide may be utilized, for example, either in the form of the pure hydroperoxide or in the term of a crude reaction mixture obtained by the oxidation. To obtain the hydroperoxide in a concentrated form, the crude oxidation reaction mixture may be stripped of unreacted nitrarted hydrocarbon by distillation at pressures of about 1 to about mm. of mercury/sq. cm. Other methods which may be used to concentrate the hydroperoxides involve solvent extraction, and precipitation with a concentrated aqueous solution (25-40%) of sodium hydroxide.

The hydroperoxides of this invention, therefore, may be decomposed when in the pure state and also when contained in mixtures with varying amounts of other organic materials. Any of the hydroperoxide materials may be dissolved in a suitable organic solvent which. is inert to any of the reactants, products or reaction conditions involved in the process of this invention. The solvent should be nonreactive under the conditions of reaction to the hydroperoxide, the catalyst and any of the phenolic or carbonylic reaction products obtained by the decomposition. Exemplary of such solvents are the aliphatic, cycloaliphatic, and aromatic hydrocarbons, alcohols, ketones, ethers, esters, and liquid chlorinated hydrocarbons. Exemplary of these solvents are pentane, hexane, benzene, toluene, xylene, cumene, chloroform, carbon tetrachloride, ethanol, acetone, methyl acetate, diethyl ether, and the like. In addition, various acidic solvents such as glacial acetic acid which may exert some catalytic activity may be used. When used, the amount of other catalyst may be reduced. The concentration of the solvent and the hydroperoxide in the solution is limited only by the reactivity of the hydroperoxide during the decomposition, the efiectiveness of the catalyst, and the temperature and pressure used.

The decomposition reaction also may be carried out in the vapor phase. The hydroperoxide may be vaporized and brought into intimate contact with the catalyst and the decomposition will readily occur. The vapor process is advantageous in that the nitrophenol produced can be vaporized immediately from the reaction zone.

The decomposition reaction of this invention may be carried out either, under substantially anhydrous conditions, or in the presence of an aqueous phase. There may be used in the process any catalyst capable of decomposing the nitrated hydroperoxide to the corresponding nitrophenol. Generally illustrative of such catalysts are those materials kown as condensation catalysts, particularly the acidic condensation catalysts. The examples have shown the use of an acid treated bentonite and sulfuric acid but also found operable in the process are catalysts such as anhydrous ferric chloride, boron trifluoride, montmorillonite, kaolinite, vermiculite, silica gel, kaolin, fullers earth, diatomaceous earth, halloysite, trichloroacetic acid, picric acid, dichloroacetic acid, chloroacetic acid; sulfonic acids such as benzenesulfonic acid, p-toluene-sulfonic acid, and sulfonated phenol-formaldehyde and styrene-d-ivinylbenzene polymers; cracking catalysts such as phosphoric acid-on-alumina; and various phosphorous compounds such as phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride. All of these catalysts are illustrative of the class of catalysts known as acidic condensation catalysts. Included within this class are various materials such as the ilicates, silica gel, kieselguhr, hydrosilicates, and bauxite which are surface-active substances composed of basic compounds but which have smficient acidic surface activity to render them operable in the process. Also included are the Friedel-Crafts catalysts such as aluminum chloride, ferric chloride, boron trifluoride, zinc chloride, stannic chloride, and magnesium chloride, all of which may be supported on a carrier, which itself may have catalytic activity; other supported catalysts such as phosphoric acid on fullers earth or silica; inorganic acids, for ex ample, hydrogen chloride or sulfuric acid; and organic acids, for example, acetic acid, propionic acid, trinitroacetic acid, mononitroacetic acid, picric acid, benzenesulfonic acid, and p-toluenesulfonic acid.

- The concentration of the catalyst based on the hydroperoxide will depend on the reactivity of the catalyst, the temperature of reaction, the desired reaction time and the mode of operation. In a batch decomposition process, the concentration generally may be from about 0.01% to about 200%. A preferable catalyst concentration on this basis is from about 1% to about 20%, and a particularly applicable amount in most instances is about 5%. In the case of those catalysts wherein it is possible to calculate their molar concentrations relative to the hydroperoxide, the range of catalyst concentration may be expressed as from about 0.01 mole percent to about 200 mole percent based on the hydroperoxide, a preferable range on this basis being from about 1% to about 10%. In a continuous operation the ratio of catalyst to hydroperoxide at any particular instant may be as high as 100 to 1, depending upon the design of the reactor, the size of the catalyst particles, and the rate of flow of the hydroperoxide over the catalyst bed.

When the decomposition is carried out under conditions involving an aqueous phase, a water-soluble acid is preferably used. Both inorganic and organic watersoluble acids are operable. Exemplary of the inorganic acids are hydrochloric, sulfuric and phosphoric acids and the organic acids may be exemplified by the organic sulfonic acids such as p-toluenesulfonic acid. It is desirable that the concentration of the acid in the aqueous phase -be at least 20% by Weight, a preferable range on this basis being from 20 to about 65%. Particularly applicable is a concentration range from 20 to about 50%. Concentrations of acid below 20% by weight produce lower yields and require appreciably longer reaction times.

The temperature may be varied, depending principally upon the activity of the catalyst. In general, the decomposition reaction may be effected over a temperature range of about C. to about 400 C. When using anhydrous conditions, a preferable range is about 0 C. to about 200 C. When using an aqueous phase, a preferable range is about 15 C. to about C.

The examples have shown the decomposition reaction as being carried out at atmospheric pressure. The reaction, however, may be efiected under reduced pressure and it is obvious that it also may be carried out under pressures greater than atmospheric. A broad range of pressure conditions is possible but from a practical standpoint the reaction preferably is carried out either at atmospheric or slightly less than atmospheric pressure.

The process of decomposing the products of this invention to nitrophenols has many outstanding advantages over previous processes for the preparation of nitrophenols. The reaction is adapted to the use of inexpensive, simple equipment and the life of the equipment is long, due to the lack of corrosive reagents. Due to the fact that it is possible inthe hydroperoxides of this invention to have the nitro substituents in definite relationship to each other, it is possible through decomposition of the hydroperoxides to obtain nitrated phenols which also contain the phenolic and nitro substituents in definite relationship to each other. This is a definite advantage over prior processes in which a mixture of isomers always was obtained. A further advantage of the decomposition process is that it may be combined with the oxidation process for preparation of the hydroperoxides in such a manner that a continuous process may be carried out. One of the overall processes involved in this invention comprises the alkylation of benzene with propylene to obtain cumene, nitration of cumene to obtain p-nitrocumene, oxidation of the p-nitrocumene to obtain a,a-dimethyl-p-nitrobenzyl hydroperoxide, decomposition of this hydroperoxide to obtain p-nitrophenol and acetone as products, separation of the p-nitrophenol and acetone from the reaction mixture and recycle of any p-nitrocumene remaining after the decomposition step to the oxidation system after first removing any contaminating p-nitrophenol, the latter being an inhibitor for the oxidation. Preferably, it is desirable to remove by distillation, for example, the major portion of unreacted p-nitrocumene immediately following the oxidation step.

The decomposition of the hydroperoxides of this in vention represents a more economical and efficient means for obtaining nitrophenols. Due to the simple nature of the process, it will be found particularly applicable to small scale installations and will not require the vast outlay of capital and equipment required by previous processes.

In addition, the hydroperoxides of this invention may be easily converted to the corresponding acetophenone. Thus, when a,a-dimethyl-p-nitrobenzyl hydroperoxide is treated with a ferrous salt such as FeSO4 there is produced p-nitroacetophenone. On the other hand, if the hydroperoxides of this invention are treated with hydrogen or an inorganic reducing salt such as sodium sulfide, sodium sulfite, etc., the hydroperoxide is reduced to the corresponding alcohol. For example, a,a-dimethylp-nitrobenzyl hydroperoxide is reduced to u,u-dimethylp-nitrobenzyl alcohol.

The hydroperoxides of this invention are also very useful as catalysts in both the emulsion and homogeneous polymerization of unsaturated compounds such as styrene and butadiene.

This application constitutes a division of my application for Letters Patent Serial No. 188,645 filed October 5, 1950, now Patent 2,718,530.

What I claim and desire to protect by Letters Patent is:

l. The process of preparing a nitrophenol from an organic compound containing an aromatic hydrocarbon nucleus having attached to the ring thereof at least one nitro group and at least one alkyl group having at least two carbon atoms and at least one hydrogen atom on the carbon atom alpha to the aromatic ring, which comprises passing an oxygen-containing gas through said organic compound in liquid phase under noncatalytic conditions 10 to obtain the corresponding hydroperoxide, and contacting said hydroperoxide under acidic conditions with an acidic condensation catalyst to obtain said nitrophenol.

2. The process of claim 1 wherein the hydroperoxide is formed by carrying out the oxidation under anyhdrous conditions in the presence of a peroxidic free radical oxidation initiator.

3. The process of claim 1 wherein the hydroperoxide is formed by carrying out the oxidation in the presence of a separate aqueous phase.

4. The process of claim 1 wherein the hydroperoxide is formed by carrying out the oxidation in the presence of an alkaline stabilizing agent.

5. The process of claim 1 wherein the hydroperoxide is contacted with the acidic condensation catalyst under substantially anhydrous conditions.

6. The process of claim 1 wherein the hydroperoxide is contacted with the acidic condensation catalyst under conditions involving an aqueous phase.

7. The process of claim 6 wherein the aqueous phase contains between 20% and about by weight of a water-soluble acid.

8. The process of claim 1 wherein the nitrophenol prepared is p-nitrophenol and the hydroperoxide intermediate is p-nitro-a,a-diniethylbenzyl hydroperoxide.

9. The process of claim 1 wherein the nitrophenol prepared is m-nitro-p-cresol and the hydroperoxide intermediate is m-nitro-u,a-dimethyl-p-methylbenzyl hydroperoxide.

Bartlett et al.: Jour. Amer. Chem. Soc. vol. 72, pgs. 309599 (5 pgs.). Publ. July 1950; article received for publ. Sept. 8, 1949.

Kharasch et al.: Jour. Organic Chem, vol. 15, p. 749

(July 1950; 1 pg. only), article received for publication Dec. 7, 1949). 

1. THE PROCESS OF PREPARING A NITROPHENOL FROM AN ORGANIC COMPOUND CONTAINING AN AROMATIC HYDROCARBON NUCLEUS HAVING ATTACHED TO THE RING THEREOF AT LEAST ONE NITRO GROUP AND AT LEAST ONE ALKYL GROUP HAVING AT LEAST TWO CARBON ATOMS AND AT LEAST ONE HYDROGEN ATOM ON THE CARBON ATOM ALPHA TO THE AROMATIC RING, WHICH COMPRISES PASSING AN OXYGEN-CONTAINING GAS THROUGH SAID ORGANIC COMPOUND IN LIQUID PHASE UNDER NONCATALYTIC CONDITIONS TO OBTAIN THE CORRESPONDING HYDROPEROXIDE, AND CONTACTING SAID HYDROPEROXIDE UNDER ACIDIC CONDITIONS WITH AN ACIDIC CONDENSATION CATALYST TO OBTAIN SAID NITROPHENOL. 